US4929685A - Method for modifying the surface of polycarbonate resin - Google Patents
Method for modifying the surface of polycarbonate resin Download PDFInfo
- Publication number
- US4929685A US4929685A US07/217,408 US21740888A US4929685A US 4929685 A US4929685 A US 4929685A US 21740888 A US21740888 A US 21740888A US 4929685 A US4929685 A US 4929685A
- Authority
- US
- United States
- Prior art keywords
- amine
- polycarbonate resin
- acrylate
- glycidyl
- atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 18
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 10
- JHQVCQDWGSXTFE-UHFFFAOYSA-N 2-(2-prop-2-enoxycarbonyloxyethoxy)ethyl prop-2-enyl carbonate Chemical compound C=CCOC(=O)OCCOCCOC(=O)OCC=C JHQVCQDWGSXTFE-UHFFFAOYSA-N 0.000 claims abstract description 65
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 53
- 150000001412 amines Chemical class 0.000 claims abstract description 37
- 229920001577 copolymer Polymers 0.000 claims abstract description 24
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920001519 homopolymer Polymers 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 3
- 150000001334 alicyclic compounds Chemical class 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 5
- 239000000980 acid dye Substances 0.000 abstract description 17
- 230000003287 optical effect Effects 0.000 abstract description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 description 36
- 239000011347 resin Substances 0.000 description 36
- 238000012360 testing method Methods 0.000 description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 29
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 20
- 239000000975 dye Substances 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- -1 2-ethylhexyl Chemical group 0.000 description 14
- 238000002834 transmittance Methods 0.000 description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 238000004043 dyeing Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 7
- 229920002189 poly(glycerol 1-O-monomethacrylate) polymer Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000003086 colorant Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012362 glacial acetic acid Substances 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000010446 mirabilite Substances 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 5
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- KMGARVOVYXNAOF-UHFFFAOYSA-N benzpiperylone Chemical compound C1CN(C)CCC1N1C(=O)C(CC=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 KMGARVOVYXNAOF-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 229940013688 formic acid Drugs 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 239000002685 polymerization catalyst Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 3
- 239000005695 Ammonium acetate Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 229940043376 ammonium acetate Drugs 0.000 description 3
- 235000019257 ammonium acetate Nutrition 0.000 description 3
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000000986 disperse dye Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 3
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- WLDHEUZGFKACJH-UHFFFAOYSA-K amaranth Chemical compound [Na+].[Na+].[Na+].C12=CC=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=C1N=NC1=CC=C(S([O-])(=O)=O)C2=CC=CC=C12 WLDHEUZGFKACJH-UHFFFAOYSA-K 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000003578 releasing effect Effects 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 description 1
- KKAJSJJFBSOMGS-UHFFFAOYSA-N 3,6-diamino-10-methylacridinium chloride Chemical compound [Cl-].C1=C(N)C=C2[N+](C)=C(C=C(N)C=C3)C3=CC2=C1 KKAJSJJFBSOMGS-UHFFFAOYSA-N 0.000 description 1
- LHYQAEFVHIZFLR-UHFFFAOYSA-L 4-(4-diazonio-3-methoxyphenyl)-2-methoxybenzenediazonium;dichloride Chemical compound [Cl-].[Cl-].C1=C([N+]#N)C(OC)=CC(C=2C=C(OC)C([N+]#N)=CC=2)=C1 LHYQAEFVHIZFLR-UHFFFAOYSA-L 0.000 description 1
- JTKHTHJSDJUSCV-UHFFFAOYSA-N 5,5-bis(tert-butylperoxy)-1,3,3-trimethylcyclohexene Chemical compound CC1=CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 JTKHTHJSDJUSCV-UHFFFAOYSA-N 0.000 description 1
- MPVDXIMFBOLMNW-ISLYRVAYSA-N 7-hydroxy-8-[(E)-phenyldiazenyl]naphthalene-1,3-disulfonic acid Chemical compound OC1=CC=C2C=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=C1\N=N\C1=CC=CC=C1 MPVDXIMFBOLMNW-ISLYRVAYSA-N 0.000 description 1
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004420 Iupilon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000083869 Polyommatus dorylas Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229960003010 sodium sulfate Drugs 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 229940104261 taurate Drugs 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- YXZRCLVVNRLPTP-UHFFFAOYSA-J turquoise blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Cu+2].NC1=NC(Cl)=NC(NC=2C=C(NS(=O)(=O)C3=CC=4C(=C5NC=4NC=4[N-]C(=C6C=CC(=CC6=4)S([O-])(=O)=O)NC=4NC(=C6C=C(C=CC6=4)S([O-])(=O)=O)NC=4[N-]C(=C6C=CC(=CC6=4)S([O-])(=O)=O)N5)C=C3)C(=CC=2)S([O-])(=O)=O)=N1 YXZRCLVVNRLPTP-UHFFFAOYSA-J 0.000 description 1
- 239000012801 ultraviolet ray absorbent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/6426—Heterocyclic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/645—Aliphatic, araliphatic or cycloaliphatic compounds containing amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2331/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
Definitions
- the present invention relates to a method for modifying the surface of polycarbonate resin, particularly, the surface of diethylene glycol bis(allyl carbonate) copolymer resin.
- Diethylene glycol bis(allyl carbonate) copolymer resin (hereinafter referred to as ADC resin) is a transparent thermosetting resin having excellent optical properties and mechanical properties, and is used as a lens for glasses and the like (Kogyo Zairyo, Vol. 25, No. 3, pages 35-37 (1977), and U.S. Pat. No. 2,370,565).
- ADC resin is different from polymethacrylate resin and can be easily dyed in the optician shop (Kindai Megane, 1977, May, pages 118-129).
- the dye capable of being used effectively in the dyeing in the optician shop is limited to a dispersant dye, and moreover the dispersant dye solution must be used at a high temperature of at least 90° C.
- ADC resin has not hitherto been able to be dyed with an acid dye.
- the dyed ADC resin absorbs not only a light having a specific wavelength, but also light having wavelengths in the vicinity of the specific wavelength. Therefore, the ADC resin dyed with a dispersant dye has a broad transmittance curve.
- Such dyed resin can not satisfactory be used in an industrial instrument requiring a high vividness of color.
- liquid crystal is recently used in the OA instrument and indicator, and hence the colored sheet or dyed sheet to be used in these instruments is demanded to have a sharp transmittance curve.
- the inventors have made various investigations and experiments, and found out that an ADC resin having excellent dyeability and being able to be dyed with acid dye can be obtained by modifying the surface of the ADC resin, and accomplished the present invention.
- the present invention provides a method for modifying the surface of an ADC resin so as to be dyed with acid dye.
- the dyeing with acid dye results in a dyed product having a sharp transmittance curve more easily than dyeing with dispersant dye. That is, the present invention gives a dyeability to an ADC resin so as to be dyed with acid dye and to easily obtain a dyed product having excellent optical properties.
- One of the features of the present invention lies in a method for modifying the surface of a polycarbonate resin, comprising modifying the surface of a polycarbonate resin consisting of a copolymer of 99-50% by weight of component (A) and 1-50% by weight of component (B) with an amine having an active hydrogen atom,
- said component (A) being diethyleneglycol bis(allyl carbonate), and
- component (B) being one member of monomers of glycidyl acrylate or glycidyl methacrylate, homopolymers thereof and copolymers thereof with a monomer copolymerizable therewith.
- Another feature of the present invention lies in a method for modifying the surface of a polycarbonate resin, comprising modifying the surface of a polycarbonate resin consisting of a copolymer of 99-50% by weight of component (A), 1-50% by weight of component (B), and 0-49% by weight of at least one of components (C) and (D) with an amine having an active hydrogen atom,
- said component (A) being diethylene glycol bis(allyl carbonate),
- component (B) being one member of monomers of glycidyl acrylate or glycidyl methacrylate, homopolymers thereof and copolymers thereof with a monomer copolymerizable therewith,
- component (C) being an active vinyl monomer copolymerizable with component (A) or (B), and
- component (D) being a polymer which can be dissolved or dispersed in component (A), (B) or (C).
- component (A) to be used in the present invention there can be used commercially available ordinary diethylene glycol bis(allyl carbonate).
- Component (A) is used in an amount of 99-50% by weight based on the total amount of the mixture of components (A) and (B), or components (A), (B) and at least one of (C) and (D).
- the amount of component (A) is less than 50% by weight, the resulting copolymer is poor in the characteristic properties, such as transparency, optical properties, impact resistance, solvent resistance, heat resistance, dyeability and the like, inherent to the compound of component (A), and even when the amount of component (A) is more than 99%, the resulting copolymer has not remarkably improved dyeability.
- component (B) there can be used monomers of glycidyl acrylate or glycidyl methacrylate, homopolymers of glycidyl acrylate or glycidyl methacrylate, and copolymers of glycidyl acrylate or glycidyl methacrylate with a monomer copolymerizable therewith, in which copolymer the amount of glycidyl acrylate monomer units or glycidyl methacrylate monomer units is at least 2% by weight.
- linear alkyl(C: 1 ⁇ 22) (meth)acrylates there can be used linear alkyl(C: 1 ⁇ 22) (meth)acrylates, (hereinafter, the term "(meth)acrylate” means acrylate or methacrylate), such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate and the like; branched alkyl(C: 3 ⁇ 18) (meth)acrylates, such as 2-ethylhexyl (meth)acrylate, isostearyl (meth)acrylate and the like; cyclic alkyl(C: 3 ⁇ 10) (meth)acrylates, such as cyclohexyl (meth)acrylate and the like; hydroxyalkyl(C: 2 ⁇ 10) (meth)acrylates, such as hydroxye
- the molecular weight of the homopolymer or copolymer to be used as component (B) is not particularly limited, but the homopolymers or copolymers having a weight average molecular weight of about 1,000-1,000,000 are generally used.
- Component (B) is used in an amount of 1-50% by weight, preferably 5-30% by weight, based on the total amount of the mixture of components (A) and (B), or components (A), (B) and at least one of (C) and (D) under a condition that the resulting polycarbonate resin contains 1-50% by weight, preferably 5-30% by weight, of glycidyl acrylate or glycidyl methacrylate monomer units.
- the amount of component (B) is more than 50% by weight, the resulting polycarbonate resin is poor in the physical properties.
- a polycarbonate resin having a content of glycidyl acrylate or glycidyl methacrylate monomer units lower than 1% by weight is very poor in the dyeability, and a polycarbonate resin having a content of glycidyl acrylate or methacrylate monomer units higher than 50% by weight is poor in the mold releasing property, optical property, solvent resistance and the like. Therefore, a polycarbonate resin having a content of glycidyl acrylate or methacrylate monomer units lower than 1% by weight or higher than 50% by weight is not preferably used in the present invention.
- (meth)acrylates of alkyl alcohols or aryl alcohols for example, linear alkyl(C: 1 ⁇ 22) (meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate and the like; branched alkyl(C: 3 ⁇ 18) (meth)acrylates, such as 2-ethylhexyl (meth)acrylate, isostearyl (meth)acrylate and the like; cyclic alkyl(C: 3 ⁇ 10) (meth)acrylates, such as cyclohexyl (meth)acrylate and the like; hydroxyalkyl(C: 2 ⁇ 10) (meth)acrylates, such as hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylate
- component (C) there can be used polyfunctional monomers, such as di-(meth)acrylate of polyoxyalkylene bisphenol A, (meth)acrylate of trimethylolpropane, (meth)acrylate of pentaerythritol or dipentaerythritol, and the like.
- component (D) there can be used homopolymers or copolymers of the monomers used in the above described component (C), and further commercially available polymers, such as polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polycarbonate, polyethylene, polypropylene, polybutadiene and the like, which can be dissolved or dispersed in the diethyleneglycol bis(allyl carbonate) monomer of component (A), in the compounds of component (B) or in the copolymeriable vinyl monomer of component (C).
- polymers such as polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polycarbonate, polyethylene, polypropylene, polybutadiene and the like, which can be dissolved or dispersed in the diethyleneglycol bis(allyl carbonate) monomer of component (A), in the compounds of component (B) or in the copolymeriable vinyl monomer of component (C).
- Component (D) may be used by directly dissolving or dispersing in components (A), (B) and/or (C) or may be used by previously dissolving in other solvent, adding the resulting solution of component (D) to components (A), (B) and/or (C), and then distilling off the solvent.
- Components (C) and (D) are used alone or in admixture in a total amount of components (C) and/or (D) of 0-49% by weight, preferably 0-20% by weight, based on the total amount of the mixture of components (A), (B) and at least one of (C) and (D) in view of the characteristic properties of the resulting ADC resin.
- the ADC resin In the production of the ADC resin according to the present invention, given amounts of components (A) and (B), or components (A), (B) and at least one of (C) and (D) are mixed depending upon the use purpose of the resulting ADC resin, and the resulting mixture is heated and polymerized.
- the polymerization catalyst there are used diisopropyl peroxydicarbonate, benzoyl peroxide, dicumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexene and other polymerization catalysts.
- polymerization catalysts are used in an amount of 1-5% by weight based on the total amount of the mixture of components (A) and (B), or components (A), (B) and at least one of (C) and (D).
- the polymerization temperature is varied depending upon the decomposition temperature of the polymerization catalyst, but is generally within the range of from room temperature to about 130° C.
- the polymerization time is varied depending upon the shape, thickness, dimension and the like of the resulting ADC resin, but is generally within the range of about 2-24 hours.
- the reaction mass shrinks during the polymerization reaction to form cracks in the resulting ADC resin, and hence the yield of the resin is decreased and an ADC resin having a smooth surface is not obtained.
- the polymerization temperature and time can be relatively easily selected so as to obtain an ADC resin in a high yield.
- an ADC resin having a flat sheet shape, rod shape, cylindrical shape having a semi-circular cross-section, concave or convex lens shape or the like can be obtained by selecting properly the mold, into which the ADC resin is poured.
- the surface of the resulting ADC resin is modified by using an amine having an active hydrogen atom
- the amines having an active hydrogen atom include amines having the following general formulae (I) and (II): ##STR1## wherein R 1 and R 2 may be same or different, and represent hydrogen atoms, linear or branched alkyl groups having 1-8 carbon atoms, alkanol groups having 1-8 carbon atoms, residues of alicyclic or aromatic compound having 3-8 carbon atoms, and residues of a compound having 2-10 atoms in the total number of carbon and nitrogen atoms, and ##STR2## where R 3 represents a residue of a compound having 2-10 atoms in the total number of carbon and nitrogen atoms.
- amines include ammonia, linear alkylamines, such as monomethylamine, dimethylamine, monoethylamine, diethylamine, monopropylamine, dipropylamine, monobutylamine, dibutylamine, monohexylamine, dihexylamine, monooctylamine, dioctylamine and the like; branched alkylamines, such as monoisopropylamine, diisopropylamine, mono-2-ethylhexylamine, di-2-ethylhexylamine and the like; alkanolamines, such as monoethanolamine, diethanolamine and the like; cyclohexylamine, aniline, ethylenediamine, hexamethylenediamine, triethylenetetramine, phenylenediamine, piperazine, peperidine, pyrrole, imidazole and the like.
- linear alkylamines such as monomethylamine, dimethylamine, monoe
- the modification of the surface of ADC resin by an amine having an active hydrogen atom is carried out by a process, wherein the ADC resin is immersed in the amine itself or in a solution of the amine, and treated therein at a temperature of 50°-100° C. for 1-180 minutes to react the glycidyl group present in the resin surface with the amine.
- the amine can be used in the form of a solution of the amine in water or in a solvent depending upon the property of the amine. In this case, it is preferable that the concentration of amine in the solution is at least 25% by weight.
- the solvent there can be used hydrocarbons, such as cyclohexane, benzene, toluene and the like; alcohols, such as ethanol, n-propanol, n-butanol, n-hexanol, cyclohexanol, octanol and the like; ketones, such as methyl ethyl ketone, methyl butyl ketone and the like; polyhydric alcohols and their derivatives, such as ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monoacetate, ethylene glycol diacetate and the
- the resulting surface-modified ADC resin can be easily dyed with an ordinary acid dye.
- the surface-modified ADC resin can be easily dyed by treating the resin in a dye solution containing an acid dye and a dyeing assistant of at least one of ammonium acetate, glacial acetic acid, formic acid, sodium sulfate and a surfactant at a bath temperature of 50°-100° C. for 1-180 minutes.
- the acid dyes are, for example, Kayakalan Orange RL, Kayacyl Rubinol 3GS, Kayanol Blue NR, Kayalon Navy Blue NB-E, which are sold by Nippon Kayaku Co., Ltd., and the like.
- a translucent or opaque ADC resin which can be dyed in a vivid color, can be obtained by selecting properly the polymer or monomer to be copolymerized with diethylene glycol bis(allyl carbonate) depending upon the purpose.
- additives such as antioxidant, ultraviolet ray absorbent, mold releasing agent, pigment, organic or inorganic filler and the like, can be added to the mixture of the components at the copolymerization so as to obtain an ADC resin containing these additives depending upon the purpose.
- active groups to react with acid dye can be derived from the reaction of the epoxides of glycidyl (meth)acrylate with the amine, and introduced into only the surface of an ADC resin without decreasing its physical properties.
- the surface-modified ADC resin according to the present invention can be dyed with not only disperse dye, but also acid dye. Therefore, various kinds of dyes can be used, and a color tone can be selected from wide range, and hence the ADC resin can be used in a wide field. Moreover, since a dyed product having a sharp transmittance curve can be easily obtained, the dyed product can be satisfactorily used in industrial instruments requiring high vividness of color. Accordingly, the present invention is very valuable in industry.
- a polyvinyl chloride gasket having a diameter of 2 mm was interposed between a pair of previously cleaned glass plates (sold by Nippon Sheet Glass Co., Ltd., 500 mm ⁇ 500 mm ⁇ 6 mm) and fixed between them by means of a clip to form a mold.
- the above obtained homogeneous mixture was poured into the mold, and polymerized for 15 hours in an incubator according to a temperature-rising schedule from room temperature (25° C.) to 100° C., wherein the mixture was kept at room temperature (25° C.) for 30 minutes, at 45°-50° C. for 7 hours, at 55°-60° C. for 3 hours, at 65°-70° C. for 2 hours, at 80°-85° C. for 2 hours, and at 95°-100° C. for 30 minutes.
- the cured product was then taken out of the mold, and a test piece of 50 mm square was cut out from the cured product. This test piece was treated at 70° C. for 30 minutes in a 28% aqueous ammonia solution to obtain a surface-modified product.
- the transmittance of the above treated test piece was measured within the wavelength range of 400-700 mm by means of a spectrophotometer, it was found that the test piece had transmittances of 4% at 400 nm, 3% at 490 nm, 5% at 500 nm, 35% at 550 nm, 83% at 580 nm and 88% at 600 nm. Therefore, it was ascertained that the test piece had been satisfactorily dyed.
- CR-39 diethylene glycol bis(ally carbonate) (sold by PPG Industries Inc., trademark)
- GMA glycidyl methacrylate
- ADA-200 diacrylate of an addition product of 4 mol of ethylene oxide to bisphenol A
- test pieces were prepared from the resulting polymer without carrying out an amine treatment.
- One of the test pieces was dyed with 0.05 g of a disperse dye of Kayalon Navy Blue NB-E (sold by Nippon Kayaku K.K.), which was dispersed in 100 ml of water together with 0.015 g of acetic acid, 0.069 g of sodium acetate and 0.1 g of Diapon T (trademark of sodium N-tallow fatty acid-N-methyl taurate sold by Nippon Oil & Fats Co., Ltd.), at 90° C. for 30 minutes in the same manner as described in Example 1.
- the other test piece was dyed with an acid dye of Kayanol Blue NR in the same manner as described in Example 1.
- the transmittance of the dyed test pieces was measured by means of a spectrophotometer. As the result, it was found that the test piece was dyed with the disperse dye, but the test piece was not dyed with the acid dye.
- test piece was produced in the same manners as described in Example 1.
- test piece was dyed with an acid dye without carrying out an amine treatment, the test piece was not substantially dyed.
- test piece was produced in the same manners as described in Example 1.
- the surface of the test piece was erroded with the amine to be formed into an uneven surface, and hence the test piece was no longer suitable to be used in the optical purpose.
- diethylene glycol bis(allyl carbonate) (trademark: CR-39, sold by PPG Industries, Inc.) was dissolved 10 g of a homopolymer (weight average molecular weight: 1,500) of glycidyl methacrylate and then 3 g of benzoyl peroxide was added to the solution, and the resulting mixture was homogeneously mixed.
- a polyvinyl chloride gasket having a diameter of 2 mm was interposed between a pair of previously cleaned glass plates (220mm length ⁇ 180 mm width ⁇ 6 mm thickness), and was fixed between them by means of a double clip to form a mold.
- the above obtained homogeneous mixture was poured into this mold and polymerized in an incubator according to a polymerization schedule, wherein the mixture was kept at 70° C. for 13 hours and then kept at 115° C. for 2 hours. Then, the cured product was taken out from the mold, and a test piece of 50 mm square was cut out from the cured product. This test piece was treated at 70° C. for 30 minutes in 100% monoethanolamine to obtain a surface-modified product.
- Example 26 Polymerizations, amine treatments and dyeings were carried out in the same manners as described in Example 26. The raw materials, treating conditions and obtained results are shown in Table 2 together with those of Example 26.
- the amount of component (A) is small, and therefore although a copolymer having a smooth surface was obtained in the polymerization, the copolymer was erroded at its surface during the amine treatment, and was not able to be finished into a smooth surface.
- CR-39 diethylene glycol bis(allyl carbonate) (sold by PPG Industries Inc., trademark)
- GMA glycidyl methacrylate
- PMMA polymethyl methacrylate
- PC polycarbonate (average polymerization degree n ⁇ 7, trademark: Iupilon AL, sold by Mitsubishi Gas Chemical Co., Inc.)
- a copolymer was produced from diethylene glycol bis(allyl carbonate) (trademark: CR-39) and glycidyl methacrylate (abbreviated as GMA) in a mixing ratio of CR-39/GMA of 90/10, and a test piece of 30 mm length ⁇ 20 mm width ⁇ 1.5 mm thickness was produced from the copolymer and treated with monoethanolamine in the same manners as describe in Example 11.
- the amine-treated test piece was dyed with acid dyes shown in Table 3 in the following manner.
- the amine-treated test piece was put into a test tube of 24 ⁇ mm diameter ⁇ 200 mm length, and 20 g of each of the dye solutions I-IV, which had the following compositions, was added to the test tube. Then, the test tube was immersed for 30 minutes in a bath kept at about 92° C. to obtain a dyed resin sheet.
- the transmittance of each of the dyed test pieces was measured within the wavelength range of 400-700 nm by means of a spectrophometer. The obtained results are shown in Table 3.
- Table 3 the dyeability of the dye is evaluated according to the following transmittance at the specific wavelength inherent to the dye, at which the largest amount of light is absorbed.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A polycarbonate resin of a copolymer of diethyleneglycol bis(allyl carbonate) with one of glycidyl acrylate and glycidyl methacrylate, its homopolymer and its copolymer, and further occasionally a copolymerizable compound can be easily modified with active amine at its surface, and the surface-modified copolymer of diethylene glycol bis(allyl carbonate) with glycidyl acrylate or methacrylate can be easily dyed with acid dye in a sharp color tone and can be used in an optical instrument demanded to have a high vividness of color.
Description
(1) Field of the Invention:
The present invention relates to a method for modifying the surface of polycarbonate resin, particularly, the surface of diethylene glycol bis(allyl carbonate) copolymer resin.
(2) Related Art Statement:
Diethylene glycol bis(allyl carbonate) copolymer resin (hereinafter referred to as ADC resin) is a transparent thermosetting resin having excellent optical properties and mechanical properties, and is used as a lens for glasses and the like (Kogyo Zairyo, Vol. 25, No. 3, pages 35-37 (1977), and U.S. Pat. No. 2,370,565). ADC resin is different from polymethacrylate resin and can be easily dyed in the optician shop (Kindai Megane, 1977, May, pages 118-129).
However, the dye capable of being used effectively in the dyeing in the optician shop is limited to a dispersant dye, and moreover the dispersant dye solution must be used at a high temperature of at least 90° C.
ADC resin has not hitherto been able to be dyed with an acid dye. When ADC resin is dyed with a commonly used dispersant dye, the dyed ADC resin absorbs not only a light having a specific wavelength, but also light having wavelengths in the vicinity of the specific wavelength. Therefore, the ADC resin dyed with a dispersant dye has a broad transmittance curve. Such dyed resin can not satisfactory be used in an industrial instrument requiring a high vividness of color. Particularly, liquid crystal is recently used in the OA instrument and indicator, and hence the colored sheet or dyed sheet to be used in these instruments is demanded to have a sharp transmittance curve.
The inventors have made various investigations and experiments, and found out that an ADC resin having excellent dyeability and being able to be dyed with acid dye can be obtained by modifying the surface of the ADC resin, and accomplished the present invention.
The present invention provides a method for modifying the surface of an ADC resin so as to be dyed with acid dye. In general, the dyeing with acid dye results in a dyed product having a sharp transmittance curve more easily than dyeing with dispersant dye. That is, the present invention gives a dyeability to an ADC resin so as to be dyed with acid dye and to easily obtain a dyed product having excellent optical properties.
One of the features of the present invention lies in a method for modifying the surface of a polycarbonate resin, comprising modifying the surface of a polycarbonate resin consisting of a copolymer of 99-50% by weight of component (A) and 1-50% by weight of component (B) with an amine having an active hydrogen atom,
said component (A) being diethyleneglycol bis(allyl carbonate), and
said component (B) being one member of monomers of glycidyl acrylate or glycidyl methacrylate, homopolymers thereof and copolymers thereof with a monomer copolymerizable therewith.
Another feature of the present invention lies in a method for modifying the surface of a polycarbonate resin, comprising modifying the surface of a polycarbonate resin consisting of a copolymer of 99-50% by weight of component (A), 1-50% by weight of component (B), and 0-49% by weight of at least one of components (C) and (D) with an amine having an active hydrogen atom,
said component (A) being diethylene glycol bis(allyl carbonate),
said component (B) being one member of monomers of glycidyl acrylate or glycidyl methacrylate, homopolymers thereof and copolymers thereof with a monomer copolymerizable therewith,
said component (C) being an active vinyl monomer copolymerizable with component (A) or (B), and
said component (D) being a polymer which can be dissolved or dispersed in component (A), (B) or (C).
As component (A) to be used in the present invention, there can be used commercially available ordinary diethylene glycol bis(allyl carbonate). Component (A) is used in an amount of 99-50% by weight based on the total amount of the mixture of components (A) and (B), or components (A), (B) and at least one of (C) and (D). When the amount of component (A) is less than 50% by weight, the resulting copolymer is poor in the characteristic properties, such as transparency, optical properties, impact resistance, solvent resistance, heat resistance, dyeability and the like, inherent to the compound of component (A), and even when the amount of component (A) is more than 99%, the resulting copolymer has not remarkably improved dyeability.
As component (B), there can be used monomers of glycidyl acrylate or glycidyl methacrylate, homopolymers of glycidyl acrylate or glycidyl methacrylate, and copolymers of glycidyl acrylate or glycidyl methacrylate with a monomer copolymerizable therewith, in which copolymer the amount of glycidyl acrylate monomer units or glycidyl methacrylate monomer units is at least 2% by weight. As the monomer to be used together with glycidyl acrylate or glycidyl methacrylate in component (B), there can be used linear alkyl(C: 1˜22) (meth)acrylates, (hereinafter, the term "(meth)acrylate" means acrylate or methacrylate), such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate and the like; branched alkyl(C: 3˜18) (meth)acrylates, such as 2-ethylhexyl (meth)acrylate, isostearyl (meth)acrylate and the like; cyclic alkyl(C: 3˜10) (meth)acrylates, such as cyclohexyl (meth)acrylate and the like; hydroxyalkyl(C: 2˜10) (meth)acrylates, such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate and the like; mono- or di-(meth)acrylates of a polyalkylene glycol, such as diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol or the like, which is a condensation product of 2-100 mols of alkylene glycols having 2-4carbon atoms; and vinyl monomers, such as vinyl toluene, vinyl acetate, vinyl propionate, acrylonitrile, methacrylonitrile, vinyl chloride, ethylene, propylene, butadiene, acrylamide, methacrylamide, vinylpyrolidone and the like.
The molecular weight of the homopolymer or copolymer to be used as component (B) is not particularly limited, but the homopolymers or copolymers having a weight average molecular weight of about 1,000-1,000,000 are generally used.
Component (B) is used in an amount of 1-50% by weight, preferably 5-30% by weight, based on the total amount of the mixture of components (A) and (B), or components (A), (B) and at least one of (C) and (D) under a condition that the resulting polycarbonate resin contains 1-50% by weight, preferably 5-30% by weight, of glycidyl acrylate or glycidyl methacrylate monomer units. When the amount of component (B) is more than 50% by weight, the resulting polycarbonate resin is poor in the physical properties. Moreover, a polycarbonate resin having a content of glycidyl acrylate or glycidyl methacrylate monomer units lower than 1% by weight is very poor in the dyeability, and a polycarbonate resin having a content of glycidyl acrylate or methacrylate monomer units higher than 50% by weight is poor in the mold releasing property, optical property, solvent resistance and the like. Therefore, a polycarbonate resin having a content of glycidyl acrylate or methacrylate monomer units lower than 1% by weight or higher than 50% by weight is not preferably used in the present invention.
As component (C), there can be used (meth)acrylates of alkyl alcohols or aryl alcohols, for example, linear alkyl(C: 1˜22) (meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate and the like; branched alkyl(C: 3˜18) (meth)acrylates, such as 2-ethylhexyl (meth)acrylate, isostearyl (meth)acrylate and the like; cyclic alkyl(C: 3˜10) (meth)acrylates, such as cyclohexyl (meth)acrylate and the like; hydroxyalkyl(C: 2˜10) (meth)acrylates, such as hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylate and the like; mono- or di-(meth)acrylates of a polyalkylene glycol, such as diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol or the like, which is a condensation product of 2-100 mols of alkylene glycols having 2-4 carbon atoms; and active vinyl monomers, such as styrene, vinyltoluene, vinyl acetate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinylpyrolidone and the like.
Further, as component (C), there can be used polyfunctional monomers, such as di-(meth)acrylate of polyoxyalkylene bisphenol A, (meth)acrylate of trimethylolpropane, (meth)acrylate of pentaerythritol or dipentaerythritol, and the like.
As component (D), there can be used homopolymers or copolymers of the monomers used in the above described component (C), and further commercially available polymers, such as polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polycarbonate, polyethylene, polypropylene, polybutadiene and the like, which can be dissolved or dispersed in the diethyleneglycol bis(allyl carbonate) monomer of component (A), in the compounds of component (B) or in the copolymeriable vinyl monomer of component (C). Component (D) may be used by directly dissolving or dispersing in components (A), (B) and/or (C) or may be used by previously dissolving in other solvent, adding the resulting solution of component (D) to components (A), (B) and/or (C), and then distilling off the solvent.
Components (C) and (D) are used alone or in admixture in a total amount of components (C) and/or (D) of 0-49% by weight, preferably 0-20% by weight, based on the total amount of the mixture of components (A), (B) and at least one of (C) and (D) in view of the characteristic properties of the resulting ADC resin.
In the production of the ADC resin according to the present invention, given amounts of components (A) and (B), or components (A), (B) and at least one of (C) and (D) are mixed depending upon the use purpose of the resulting ADC resin, and the resulting mixture is heated and polymerized. As the polymerization catalyst, there are used diisopropyl peroxydicarbonate, benzoyl peroxide, dicumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexene and other polymerization catalysts. These polymerization catalysts are used in an amount of 1-5% by weight based on the total amount of the mixture of components (A) and (B), or components (A), (B) and at least one of (C) and (D). The polymerization temperature is varied depending upon the decomposition temperature of the polymerization catalyst, but is generally within the range of from room temperature to about 130° C. The polymerization time is varied depending upon the shape, thickness, dimension and the like of the resulting ADC resin, but is generally within the range of about 2-24 hours. In the conventional methods, unless a multistage heating pattern is used with respect to the polymerization temperature and time, the reaction mass shrinks during the polymerization reaction to form cracks in the resulting ADC resin, and hence the yield of the resin is decreased and an ADC resin having a smooth surface is not obtained. However, according to the present invention, when a homopolymer or copolymer is used as component (B) or a polymer of component (D) is used in the starting component mixture, the polymerization temperature and time can be relatively easily selected so as to obtain an ADC resin in a high yield. Moreover, an ADC resin having a flat sheet shape, rod shape, cylindrical shape having a semi-circular cross-section, concave or convex lens shape or the like can be obtained by selecting properly the mold, into which the ADC resin is poured.
The surface of the resulting ADC resin is modified by using an amine having an active hydrogen atom
The amines having an active hydrogen atom include amines having the following general formulae (I) and (II): ##STR1## wherein R1 and R2 may be same or different, and represent hydrogen atoms, linear or branched alkyl groups having 1-8 carbon atoms, alkanol groups having 1-8 carbon atoms, residues of alicyclic or aromatic compound having 3-8 carbon atoms, and residues of a compound having 2-10 atoms in the total number of carbon and nitrogen atoms, and ##STR2## where R3 represents a residue of a compound having 2-10 atoms in the total number of carbon and nitrogen atoms.
These amines include ammonia, linear alkylamines, such as monomethylamine, dimethylamine, monoethylamine, diethylamine, monopropylamine, dipropylamine, monobutylamine, dibutylamine, monohexylamine, dihexylamine, monooctylamine, dioctylamine and the like; branched alkylamines, such as monoisopropylamine, diisopropylamine, mono-2-ethylhexylamine, di-2-ethylhexylamine and the like; alkanolamines, such as monoethanolamine, diethanolamine and the like; cyclohexylamine, aniline, ethylenediamine, hexamethylenediamine, triethylenetetramine, phenylenediamine, piperazine, peperidine, pyrrole, imidazole and the like.
The modification of the surface of ADC resin by an amine having an active hydrogen atom is carried out by a process, wherein the ADC resin is immersed in the amine itself or in a solution of the amine, and treated therein at a temperature of 50°-100° C. for 1-180 minutes to react the glycidyl group present in the resin surface with the amine.
The amine can be used in the form of a solution of the amine in water or in a solvent depending upon the property of the amine. In this case, it is preferable that the concentration of amine in the solution is at least 25% by weight. As the solvent, there can be used hydrocarbons, such as cyclohexane, benzene, toluene and the like; alcohols, such as ethanol, n-propanol, n-butanol, n-hexanol, cyclohexanol, octanol and the like; ketones, such as methyl ethyl ketone, methyl butyl ketone and the like; polyhydric alcohols and their derivatives, such as ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monoacetate, ethylene glycol diacetate and the like; and other solvents.
The resulting surface-modified ADC resin can be easily dyed with an ordinary acid dye. For example, the surface-modified ADC resin can be easily dyed by treating the resin in a dye solution containing an acid dye and a dyeing assistant of at least one of ammonium acetate, glacial acetic acid, formic acid, sodium sulfate and a surfactant at a bath temperature of 50°-100° C. for 1-180 minutes.
The acid dyes are, for example, Kayakalan Orange RL, Kayacyl Rubinol 3GS, Kayanol Blue NR, Kayalon Navy Blue NB-E, which are sold by Nippon Kayaku Co., Ltd., and the like.
Moreover, in the present invention, a translucent or opaque ADC resin, which can be dyed in a vivid color, can be obtained by selecting properly the polymer or monomer to be copolymerized with diethylene glycol bis(allyl carbonate) depending upon the purpose.
Further, in the present invention, additives, such as antioxidant, ultraviolet ray absorbent, mold releasing agent, pigment, organic or inorganic filler and the like, can be added to the mixture of the components at the copolymerization so as to obtain an ADC resin containing these additives depending upon the purpose.
According to the present invention, active groups to react with acid dye can be derived from the reaction of the epoxides of glycidyl (meth)acrylate with the amine, and introduced into only the surface of an ADC resin without decreasing its physical properties.
The surface-modified ADC resin according to the present invention can be dyed with not only disperse dye, but also acid dye. Therefore, various kinds of dyes can be used, and a color tone can be selected from wide range, and hence the ADC resin can be used in a wide field. Moreover, since a dyed product having a sharp transmittance curve can be easily obtained, the dyed product can be satisfactorily used in industrial instruments requiring high vividness of color. Accordingly, the present invention is very valuable in industry.
The following examples are given for the purpose of illustration of this invention and are not intended as limitations thereof.
A mixture of 360 g of diethylene glycol bis(allyl carbonate) (trademark: CR-39, sold by PPG Industries, Inc.), 40 g of glycidyl methacrylate and 12 g of diisopropyl peroxydicarbonate was homogeneously mixed. A polyvinyl chloride gasket having a diameter of 2 mm was interposed between a pair of previously cleaned glass plates (sold by Nippon Sheet Glass Co., Ltd., 500 mm×500 mm×6 mm) and fixed between them by means of a clip to form a mold. The above obtained homogeneous mixture was poured into the mold, and polymerized for 15 hours in an incubator according to a temperature-rising schedule from room temperature (25° C.) to 100° C., wherein the mixture was kept at room temperature (25° C.) for 30 minutes, at 45°-50° C. for 7 hours, at 55°-60° C. for 3 hours, at 65°-70° C. for 2 hours, at 80°-85° C. for 2 hours, and at 95°-100° C. for 30 minutes. The cured product was then taken out of the mold, and a test piece of 50 mm square was cut out from the cured product. This test piece was treated at 70° C. for 30 minutes in a 28% aqueous ammonia solution to obtain a surface-modified product.
Into water were added 0.05 g of Kayakalan Orange RL (sold by Nippon Kayaku Co., Ltd.), 5 g of ammonium acetate and 2 g of glacial acetic acid, and the total amount of the resulting solution was made up to 100 ml. The solution was heated up to 90° C., and the above described surface-modified test piece was put into the heated solution and dyed therein for 5 minutes while being stirred. After dyeing, the dyed test piece was taken out from the solution, washed with water and then dried. When the transmittance of the above treated test piece was measured within the wavelength range of 400-700 mm by means of a spectrophotometer, it was found that the test piece had transmittances of 4% at 400 nm, 3% at 490 nm, 5% at 500 nm, 35% at 550 nm, 83% at 580 nm and 88% at 600 nm. Therefore, it was ascertained that the test piece had been satisfactorily dyed.
Polymerizations, amine treatments and dyeings were carried out in the same manners as described in Example 1. The raw materials, treating conditions and obtained results are shown in Table 1 together with those of Example 1.
The symbols indicating the components of copolymer in Table 1 are as follows.
CR-39: diethylene glycol bis(ally carbonate) (sold by PPG Industries Inc., trademark)
GMA: glycidyl methacrylate
GA: glycidyl acrylate
VA: vinyl acetate
MMA: methyl methacrylate
PP-1000: poly(n=7)propylene glycol monomethacrylate
PE-350: poly(n=8˜9)ethylene glycol monomethacrylate
ADP-200: poly(n=3˜4)propylene glycol diacrylate
ADA-200: diacrylate of an addition product of 4 mol of ethylene oxide to bisphenol A
i-BOMA: isobutyl methacrylate
C12 OMA: dodecyl methacrylate
When Kayacyl Rubinol 3GS or Kayanol Blue NR (both being sold by Nippon Kayaku Co., Ltd.) is used as an acid dye, the following dyeing assistants are used.
Kayacyl Rubinol 3GS
sodium sulfate 10 hydrate (Glauber's salt) 2%
formic acid 5%
Kayanol Blue NR
sodium sulfate 10 hydrate (Glauber's salt) 2%
glacial acetic acid 3%
A mixture of 400 g of diethylene glycol bis(allyl carbonate) and 12 g of diisopropyl peroxydicarbonate was polymerized in the same manner as described in Example 1.
Two test pieces were prepared from the resulting polymer without carrying out an amine treatment. One of the test pieces was dyed with 0.05 g of a disperse dye of Kayalon Navy Blue NB-E (sold by Nippon Kayaku K.K.), which was dispersed in 100 ml of water together with 0.015 g of acetic acid, 0.069 g of sodium acetate and 0.1 g of Diapon T (trademark of sodium N-tallow fatty acid-N-methyl taurate sold by Nippon Oil & Fats Co., Ltd.), at 90° C. for 30 minutes in the same manner as described in Example 1. The other test piece was dyed with an acid dye of Kayanol Blue NR in the same manner as described in Example 1.
The transmittance of the dyed test pieces was measured by means of a spectrophotometer. As the result, it was found that the test piece was dyed with the disperse dye, but the test piece was not dyed with the acid dye.
A polymerization was carried out and a test piece was produced in the same manners as described in Example 1. When the test piece was dyed with an acid dye without carrying out an amine treatment, the test piece was not substantially dyed.
A mixture of 40 g of glycidyl methacrylate and 360 g of methyl methacrylate was polymerized and a test piece was produced in the same manners as described in Example 1. When the test piece was treated in monoethanolamine at 90° C. for 30 minutes, the surface of the test piece was erroded with the amine to be formed into an uneven surface, and hence the test piece was no longer suitable to be used in the optical purpose.
The obtained results in the above Comparative examples 1, 2, 3 and 4 are also shown in Table 1.
TABLE 1
__________________________________________________________________________
Amine treatment condition
Concentra-
Temper-
Component tion ature
Time
(A), (wt %)
(B), (wt %)
(C), (wt %)
Amine (%) (°C.)
(min.)
__________________________________________________________________________
Example
1 CR-39, 90
GMA, 10
-- ammonia 28 70 30
2 CR-39, 97.5
GMA, 2.5
-- " 28 70 30
3 CR-39, 70
GMA, 30
-- " 28 70 30
4 CR-39, 50
GMA, 50
-- " 28 70 30
5 CR-39, 90
GMA, 10
-- monobutylamine
100 90 10
6 CR-39, 90
GMA, 10
-- monooctylamine
50 80 10
7 CR-39, 90
GMA, 10
-- cyclohexylamine
100 90 10
8 CR-39, 90
GMA, 10
-- aniline 100 90 10
9 CR-39, 90
GMA, 10
-- ethylenediamine
50 80 10
10 CR-39, 90
GMA, 10
-- hexamethylenediamine
50 80 10
11 CR-39, 90
GMA, 10
-- monoethanolamine
100 90 10
12 CR-39, 90
GMA, 10
-- dibutylamine
50 80 10
13 CR-39, 80
GMA, 10
MMA, 10
monoethanolamine
100 60 60
14 CR-39, 50
GMA, 10
MMA, 10
" 100 60 60
15 CR-39, 80
GMA, 10
VA, 10 " 100 60 120
16 CR-39, 80
GMA, 10
PP-1000, 10
monoethanolamine
100 70 30
17 CR-39, 80
GMA, 10
PE-350, 10
" 100 70 30
18 CR-39, 80
GA, 10
ADP-200, 10
" 100 70 30
19 CR-39, 80
GA, 10
ADA-200, 10
" 100 70 30
20 CR-39, 80
GMA, 10
i-BOMA, 10
" 100 70 30
21 CR-39, 80
GMA, 10
C.sub.12 OMA, 10
" 100 70 30
22 CR-39, 90
GMA, 10
-- piperazine 50 70 30
23 CR-39, 90
GMA, 10
-- piperidine 100 70 30
24 CR-39, 90
GMA, 10
-- pyrrole 100 70 30
25 CR-39, 90
GMA, 10
-- imidazole 50 70 30
Compar-
1 CR-39, 100
-- -- -- -- -- --
ative
2 CR-39, 100
-- -- -- -- -- --
example
3 CR-39, 90
GMA, 10
-- -- -- -- --
4 -- GMA, 10
MMA, 90
monoethanolamine
100 90 30
__________________________________________________________________________
Dyeing condition
Bath Transmittance
temper- Wave-
ature
Time length
T
Dye (°C.)
(min.)
(nm)
(%)
Remarks
__________________________________________________________________________
Example
1 Kayakalan Orange RL
90 5 490 3 aqueous ammonia solution
2 " 90 30 " 12 aqueous ammonia solution
3 " 90 5 " 1 aqueous ammonia solution
4 " 90 1 " 0 aqueous ammonia solution
5 Kayacyl Rubinol 3GS
90 10 570 5
6 " 80 10 " 8 ethylene glycol solution of amine
7 " 90 10 " 7
8 " 90 10 " 16
9 Kayanol Blue NR
80 10 610 9 aqueous amine solution
10 " 80 5 " 12 aqueous amine solution
11 " 90 5 " 0
12 " 80 5 " 11 ethylene glycol solution of amine
13 " 60 120 " 4
14 " 60 60 " 8
15 " 60 60 " 3
16 " 70 30 610 2
17 " 70 30 " 0
18 " 70 30 " 4
19 " 70 30 " 4
20 " 70 30 " 10
21 " 70 30 " 8
22 " 70 30 " 6 aqueous piperazine solution
23 " 70 30 " 12
24 " 70 30 " 10
25 " 70 30 " 7 aqueous imidazole solution
Compar-
1 Kayalon Navy Blue NB-E
92 30 590 4
ative
2 Kayanol Blue NR
80 30 610 91.5
example
3 " 80 30 " 91
4 -- -- -- -- --
__________________________________________________________________________
In 90 g of diethylene glycol bis(allyl carbonate) (trademark: CR-39, sold by PPG Industries, Inc.) was dissolved 10 g of a homopolymer (weight average molecular weight: 1,500) of glycidyl methacrylate and then 3 g of benzoyl peroxide was added to the solution, and the resulting mixture was homogeneously mixed. A polyvinyl chloride gasket having a diameter of 2 mm was interposed between a pair of previously cleaned glass plates (220mm length×180 mm width×6 mm thickness), and was fixed between them by means of a double clip to form a mold. The above obtained homogeneous mixture was poured into this mold and polymerized in an incubator according to a polymerization schedule, wherein the mixture was kept at 70° C. for 13 hours and then kept at 115° C. for 2 hours. Then, the cured product was taken out from the mold, and a test piece of 50 mm square was cut out from the cured product. This test piece was treated at 70° C. for 30 minutes in 100% monoethanolamine to obtain a surface-modified product.
Into water were added 0.05 g of Kayanol Blue NR (acid dye, sold by Nippon Kayaku Co., Ltd.), 0.1 g of sodium sulfate 10 hydrate and 0.15 g of glacial acetic acid, and the total amount of the resulting solution was made up to 100 ml. The solution was heated up to 90° C., and the above described surface-modified test piece was put into the heated solution and dyed therein for 5 minutes under stirring. After dyeing, the dyed test piece was taken out from the solution, washed with water and then dried. When the transmittance of the dyed test piece was measured within the wavelength range of 400-700 nm by means of a spectrophotometer, the following result was obtained.
______________________________________
Wavelength (nm)
Transmittance (%)
______________________________________
400 20
450 63
500 10
550 0
600 0
700 50
______________________________________
It was ascertained from the above obtained result that the cured product was satisfactorily dyed.
Polymerizations, amine treatments and dyeings were carried out in the same manners as described in Example 26. The raw materials, treating conditions and obtained results are shown in Table 2 together with those of Example 26.
In Comparative example 6, the amount of component (A) is small, and therefore although a copolymer having a smooth surface was obtained in the polymerization, the copolymer was erroded at its surface during the amine treatment, and was not able to be finished into a smooth surface.
The symbols indicating the components of copolymer in Table 2 are as follows.
CR-39: diethylene glycol bis(allyl carbonate) (sold by PPG Industries Inc., trademark)
GMA: glycidyl methacrylate
GA: glycidyl acrylate
MMA: methyl methacrylate
PGMA: polyglycidyl methacrylate
PGA: polyglycidyl acrylate
PMMA: polymethyl methacrylate
PC: polycarbonate (average polymerization degree n≃7, trademark: Iupilon AL, sold by Mitsubishi Gas Chemical Co., Inc.)
St: styrene
AN: acrylonitrile
i-BOMA: isobutyl methacrylate
TABLE 2
__________________________________________________________________________
Component
A, (wt %)
B, (wt %) C, (wt %)
D, (wt %)
__________________________________________________________________________
Example
26
CR-39, 90
PGMA (MW:1,500), 10
27
CR-39, 90
PGA (MW:10,000), 10
28
CR-39, 90
PGMA (MW:50,000), 10
29
CR-39, 80
GMA/MMA = 1/1
(MW:10,000), 20
30
CR-39, 90
GA/MMA = 1/1 (MW:10,000), 10
31
CR-39, 80
GMA/i-BOMA = 1/1
(MW:10,000), 20
32
CR-39, 90
GMA/St/MMA = 3/3/4
(MW:10,000), 10
33
CR-39, 95
GMA/St/AN = 2/6/2
(MW:10,000), 5
34
CR-39, 89
PGMA (MW:50,000), 10 PC, 1
35
CR-39, 80
PGMA (MW:50,000), 10
i-BOMA, 10
36
CR-39, 80
PGMA (MW:50,000), 10 PMMA, 10
37
CR-39, 60
GMA/MMA = 1/1
(MW:10,000), 30
MMA, 10
Compar-
5
CR-39, 90 GMA, 10
ative
6
CR-39, 30
PGMA (MW:50,000), 10 PMMA, 60
example
7
CR-39, 100
8
CR-39, 80 PMMA, 20
__________________________________________________________________________
Transmit-
tance
Appearance of a cured product sheet
Dye (%)
taken out from the mold
Treating amine
(Kayanol)
(at 600 nm)
__________________________________________________________________________
Example
26
colorless and transparent, no crack
monoethanolamine
Blue-NR
0
27
colorless and transparent, no crack
diethanolamine
Blue-NR
0
28
colorless and transparent, no crack
cyclohexylamine
Blue-NR
10
29
colorless and transparent, no crack
piperidine
Blue-NR
11
30
colorless and transparent, no crack
monoethanolamine
Blue-NR
3
31
colorless and transparent, no crack
monoethanolamine
Blue-NR
0
32
colorless and transparent, no crack
monoethanolamine
Blue-NR
12
33
pale yellow and transparent, no crack
monoethanolamine
Blue-NR
18
34
slightly white-turbid, no crack
monoethanolamine
Blue-NR
0
35
colorless and transparent, no crack
monoethanolamine
Blue-NR
0
36
colorless and transparent, no crack
monoethanolamine
Blue-NR
0
37
colorless and transparent, no crack
monoethanolamine
Blue-NR
0
Compar-
5
colorless and transparent, crack
monoethanolamine
Blue-NR
0
ative
6
colorless and transparent, no crack
monoethanolamine
Blue-NR
8
example
7
colorless and transparent, crack
monoethanolamine
Blue-NR
92
8
colorless and transparent, no crack
monoethanolamine
Blue-NR
91
__________________________________________________________________________
A copolymer was produced from diethylene glycol bis(allyl carbonate) (trademark: CR-39) and glycidyl methacrylate (abbreviated as GMA) in a mixing ratio of CR-39/GMA of 90/10, and a test piece of 30 mm length×20 mm width×1.5 mm thickness was produced from the copolymer and treated with monoethanolamine in the same manners as describe in Example 11. The amine-treated test piece was dyed with acid dyes shown in Table 3 in the following manner. The amine-treated test piece was put into a test tube of 24×mm diameter×200 mm length, and 20 g of each of the dye solutions I-IV, which had the following compositions, was added to the test tube. Then, the test tube was immersed for 30 minutes in a bath kept at about 92° C. to obtain a dyed resin sheet.
______________________________________ Composition of dye solutions ______________________________________ Dye solution I Dye 0.1% Glauber's salt 2% Formic acid 5% Water balance Dye solution II Dye 0.1% Glauber's salt 2% Formic acid 3% Water balance Dye solution III Dye 0.1% Glauber's salt 2% Glacial acetic acid 3% Water balance Dye solution IV Dye 0.1% Ammonium acetate 5% Glacial acetic acid 2% Water balance ______________________________________
The transmittance of each of the dyed test pieces was measured within the wavelength range of 400-700 nm by means of a spectrophometer. The obtained results are shown in Table 3. In Table 3, the dyeability of the dye is evaluated according to the following transmittance at the specific wavelength inherent to the dye, at which the largest amount of light is absorbed.
______________________________________
Transmittance Dyeability
______________________________________
lower than 5% ⊚
very excellent
5-10% ○
excellent
10-30% Δ
good
higher than 30% x poor
______________________________________
TABLE 3
______________________________________
Dye
Sam- solu-
ple Dye CI No. tion Dye-
No. (Trademark) (Acid) used ability
______________________________________
Kayacyl Colors
1 Brilliant Flavine FF
Y 7:1 I ⊚
2 Yellow GG Y 17 I ⊚
3 Rubinol 3GS R 37 I ⊚
4 Rhodamine FB R 52 I ⊚
5 Sky Blue R B 62 II ⊚
6 Blue HRL B 182 I ⊚
7 Pure Blue FGA B 7 I ⊚
Kayaku Polyamide Colors
8 Black 2JN III ○
Kayanol Colors
9 Yellow NFG Y 49 II ⊚
10 Yellow N5G Y 110 III ⊚
11 Yellow N3R O 67 IV ⊚
12 Red NBR R 366 III ⊚
13 Red NB R 266 III ⊚
14 Floxine NK R 257 II ⊚
15 Red 3BL R 254 III ⊚
16 Blue NR B 129 III ⊚
17 Cyanine GB B 83 III ⊚
18 Cyanine G B 90 III ⊚
19 Blue N2G B 40 II ⊚
20 Cyanine Green G G 25 III ⊚
21 Navy Blue R B 92 III ⊚
Kayanol Milling Colors
22 Yellow 5GW Y 127 IV ⊚
23 Yellow 3GW Y 72 IV ⊚
24 Yellow O O 38 IV ⊚
25 Yellow RW new O 149 IV ⊚
26 Orange G O 56 IV ⊚
27 Brown 4GW Br 13 IV ⊚
28 Brown RX O 51 IV ⊚
29 Red Brown V R 119 IV ⊚
30 Scarlet FGW R 138 IV ⊚
31 Red GRA -- IV ⊚
32 Red RS 125 R 114 IV ⊚
33 Red BW R 138 IV ⊚
34 Red 3BW R 274 IV ⊚
35 Red 6BW V 97 IV ⊚
36 Violet FBW V 48 IV ⊚
37 Blue 2RL B 140 IV ⊚
38 Ultra Sky SE B 112 IV ⊚
39 Blue BW B 138 IV ⊚
40 Blue GW B 127 III ○
41 Turquoise Blue 3G B 185 IV X
42 Green 5GW G 28 IV ⊚
43 Green GW G 27 IV ⊚
44 Cyanine 5R B 113 IV ⊚
45 Black TLR Bk 110 IV ⊚
46 Black TLB Bk 109 IV ⊚
47 Black VLG Bk 26 IV ⊚
Kayakalan Colors
48 Yellow GL 143 Y 161 IV ⊚
49 Orange RL O 122 IV ⊚
50 Brown GL Br 294 IV ⊚
51 Brown RL 143 Br 297 IV ⊚
52 Scarlet GL R 317 IV ⊚
53 Red BL R 318 IV ⊚
54 Bordeaux BL R 256 IV ○
55 Olive GL G 75 IV ⊚
56 Grey BL Bk 122 IV ⊚
57 Blue Black RL Bk 234 IV ⊚
58 Black 2RL Bk 155 IV ⊚
59 Black BGL Bk 107 IV ⊚
Kayalax Colors
60 Yellow G Y 207 IV ⊚
61 Brown GR Br 282 IV ⊚
62 Brown R Br 283 IV ⊚
63 Red G R 315 IV ⊚
64 Olive G G 73 IV ⊚
65 Navy R B 300 IV ⊚
66 Navy B B 229 IV ⊚
SANDOZ
67 Yellow E-3GL 150% Y 196 IV ⊚
68 Brilliant Red E-BL R 106 IV ⊚
69 Brilliant Green E-B 400%
G 16 IV ⊚
70 Blue 2AL 200% B 25 IV ⊚
Kayaku
71 Red 14P IV ⊚
BAYER A.G.
72 TELON Fast Red AF3G 150% IV ⊚
73 TELON Fast Red ER IV ⊚
74 TELON Red FRLL IV ⊚
75 TELON Fast Blue ESN IV ⊚
76 ALIZARIN Brilliant Blue IV ⊚
GLW
Showa Kako
77 Yellow MR Concentration
Y 42 IV ⊚
78 Red RS Concentration
R 114 IV ⊚
79 Blue 5C Concentration
B 103 IV ⊚
______________________________________
Claims (4)
1. A method for modifying the surface of a polycarbonate resin substrate, comprising the steps of:
providing a polycarbonate resin substrate, said polycarbonate resin comprising a copolymer of 50-99 wt % diethylene glycol bis(allyl carbonate), and 1-50 wt % of one member of monomers of glycidyl acrylate or glycidyl methacrylate, homopolymers thereof and copolymers thereof with a monomer copolymerizable therewith;
providing an amine, or solution thereof, having an active hydrogen atom, said amine, or solution thereof, being maintained at a temperature of about 50°-100° C.; and
immersing said polycarbonate resin substrate in said amine, or solution thereof, for about 1-180 minutes to react the glycidyl group present in the surface of the polycarbonate resin substrate with the amine.
2. A method according to claim 1, wherein said polycarbonate resin substrate is polymerized at a temperature within the range of about 20°-130° C. for about 2-24 hours.
3. A method according to claim 1, wherein said amine is one of the amines represented by the following general formula (I) and (II): ##STR3## wherein R1 and R2 may be the same or different and represent hydrogen atoms, linear or branched alkyl groups having 1-8 carbon atoms, alkanol groups having 1-8 carbon atoms, residues of alicyclic or aromatic compounds having 3-8 carbon atoms, or residues of compounds having 2-10 atoms in the total number of carbon and nitrogen atoms; and ##STR4## wherein R3 represents a residue of a compound having 2-10 atoms in the total number of carbon and nitrogen atoms.
4. A method according to claim 1, wherein the homopolymer or copolymer of glycidyl acrylate or glycidyl methacrylate contains 2-100% by weight of glycidyl acrylate monomer units or glycidyl methacrylate monomer units.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13238886A JPH0680090B2 (en) | 1986-06-07 | 1986-06-07 | Surface modification method of carbonate resin |
| JP61-132388 | 1986-06-07 | ||
| JP62174777A JPS6420242A (en) | 1987-07-15 | 1987-07-15 | Surface modification of carbonate resin |
| JP62-174777 | 1987-07-15 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/436,640 Division US5028660A (en) | 1987-07-15 | 1989-11-15 | Method for modifying the surface of polycarbonate resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4929685A true US4929685A (en) | 1990-05-29 |
Family
ID=26466973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/217,408 Expired - Fee Related US4929685A (en) | 1986-06-07 | 1988-07-11 | Method for modifying the surface of polycarbonate resin |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US4929685A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5151106A (en) * | 1990-12-21 | 1992-09-29 | Allergan, Inc. | Method for tinting a hydrophilic polymer by incorporating a reactive dye into the polymer prior to polymerization |
| US20030175325A1 (en) * | 1992-09-14 | 2003-09-18 | Chatelier Ronald Christopher | Multilayer materials |
| US20030219533A1 (en) * | 2001-11-13 | 2003-11-27 | Peter Chabrecek | Method for modifying the surface of biomedical articles |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2370565A (en) * | 1940-10-15 | 1945-02-27 | Pittsburgh Plate Glass Co | Polybasic acid-polyhydric alcohol esters and polymers thereof |
| US3518040A (en) * | 1964-11-09 | 1970-06-30 | Eastman Kodak Co | Formation of urethane units on the surface of polycarbonate structures |
| US4091048A (en) * | 1971-08-16 | 1978-05-23 | Ford Motor Company | Powder coating compositions containing glycidyl ester copolymers and organic carboxylic acid anhydride crosslinking agent |
-
1988
- 1988-07-11 US US07/217,408 patent/US4929685A/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2370565A (en) * | 1940-10-15 | 1945-02-27 | Pittsburgh Plate Glass Co | Polybasic acid-polyhydric alcohol esters and polymers thereof |
| US3518040A (en) * | 1964-11-09 | 1970-06-30 | Eastman Kodak Co | Formation of urethane units on the surface of polycarbonate structures |
| US4091048A (en) * | 1971-08-16 | 1978-05-23 | Ford Motor Company | Powder coating compositions containing glycidyl ester copolymers and organic carboxylic acid anhydride crosslinking agent |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5151106A (en) * | 1990-12-21 | 1992-09-29 | Allergan, Inc. | Method for tinting a hydrophilic polymer by incorporating a reactive dye into the polymer prior to polymerization |
| US20030175325A1 (en) * | 1992-09-14 | 2003-09-18 | Chatelier Ronald Christopher | Multilayer materials |
| US6623747B1 (en) * | 1992-09-14 | 2003-09-23 | Novartis Ag | Multilayer materials |
| US6923978B2 (en) * | 1992-09-14 | 2005-08-02 | Novartis Ag | Multilayer materials |
| US20030219533A1 (en) * | 2001-11-13 | 2003-11-27 | Peter Chabrecek | Method for modifying the surface of biomedical articles |
| US6878399B2 (en) | 2001-11-13 | 2005-04-12 | Novartis Ag | Method for modifying the surface of biomedical articles |
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